Chapter 4 - Alkenes and Alkynes

WILLIAM H.
BROWN
THOMAS POON
www.wiley.com/college/brown
CHAPTER FOUR
Alkenes and Alkynes
Copyright 2014 John Wiley & Sons, Inc. All rights reserved.
4-1
Unsaturated Hydrocarbons
Unsaturated Hydrocarbon: Contains one or

more carbon-carbon double or triple bonds or
benzene-like rings.
Alkene: contains a carbon-carbon double bond
and has the general formula CnH2n.
Alkyne: contains a carbon-carbon triple bond
and has the general formula CnH2n-2.
4-2
Unsaturated Hydrocarbons
Arene: benzene and its derivatives (Ch 9)
4-3
Benzene and Phenyl Groups
We do not study benzene and its derivatives

until Chapter 9.
However, we show structural formulas of
compounds containing a phenyl group before that
time.
The phenyl group is not reactive under any of the
conditions we describe in chapters 5-8.
4-4
Structure of Alkenes
The two carbon atoms of a double bond and

the four atoms bonded to them lie in a plane,
with bond angles of approximately 120.
4-5
Structure of Alkenes
According to the orbital overlap model, a

double bond consists of one s bond formed
by overlap of sp2 hybrid orbitals and one p
bond formed by overlap of parallel 2p
orbitals.
Rotating by 90breaks the pi bond.
4-6
Cis-Trans Isomerism
Because of restricted rotation about a CC

double bond, groups on adjacent carbons are
either cis or trans to each other.
Because of nonbonded interaction strain between
alkyl substituents of the same side of the double
bond, a trans alkene is more stable than an
isomeric cis alkene.
4-7
Structure of Alkynes
The functional group of an alkyne is a carboncarbon triple bond.

A triple bond consists of:
One s bond formed by the overlap of sp hybrid
orbitals.
Two p bonds formed by the overlap of sets of
parallel 2p orbitals.
4-8
Nomenclature of Alkenes
IUPAC Nomenclature of alkenes

Use the infix -en- to show the presence of a
carbon-carbon double bond.
Number the parent chain to give the 1st carbon of
the double bond the lower number.
Follow IUPAC rules for numbering and naming
substituents.
For a cycloalkene, the numbering of the atoms of
the ring the must begin with the two carbons of
the double bond.
4-9
IUPAC nomenclature of alkenes
1-Hexene
4-10
Some alkenes, particularly low-molecularweight ones, are known almost exclusively by

their common names.
4-11
Nomenclature of Alkynes
IUPAC nomenclature of alkynes

Use the infix -yne to show the presence of a
carbon-carbon triple bond.
Number the parent chain to give the 1st carbon of
the triple bond the lower number.
Follow IUPAC rules for numbering and naming
substituents.
4-12
Configuration: Cis-Trans
The cis-trans system: Configuration is

determined by the orientation of atoms of the
main chain.
4-13
Configuration: E,Z
To Assign an E,Z configuration, first assign a priority
to the substituents on each carbon of the double
bond.
If the groups of higher priority are on the same side of the
double bond, the configuration is Z (German: zusammen,
together).
If the groups of higher priority are on opposite sides of the
double bond, the configuration is E (German: entgegen,
opposite).
4-14
Configuration: E,Z
Priority rules
1. Priority is based on atomic number; the higher the atomic number, the
higher the priority.
2. If priority cannot be assigned on the basis of the atoms bonded

directly to the double bond, look to the next set of atoms; priority is
assigned at the first point of difference.
4-15
Configuration - E,Z
3. Atoms participating in a double or triple bond are
considered to be bonded to an equivalent
number of similar atoms by single bonds.
4-16
Configuration - E,Z
Example: Name each alkene by the E,Z

system and specify its configuration.
4-17
Cis-Trans Isomerism
The configuration of the double bond in
cyclopropene through cycloheptene must be cis.
These rings are not large enough to
accommodate a trans double bond.
Cyclooctene is the smallest cycloalkene that can
accommodate a trans double bond.
4-18
Cis-Trans Isomerism
Dienes, trienes, and polyenes
For an alkene with n carbon-carbon double bonds, each
of which can show cis-trans isomerism, 2n cis-trans
isomers are possible.
Consider 2,4-heptadiene; it has four cis-trans isomers,
two of which are drawn here.
4-19
Cis-Trans Isomerism
Vitamin A has five C-C double bonds.
Four of the five can show cis-trans isomerism.
Vitamin A is the all-trans isomer.
4-20
Physical Properties
Alkenes and alkynes are nonpolar compounds.

The only attractive forces between their molecules
are dispersion forces.
The physical properties of alkenes and alkynes

are similar to those of alkanes of similar carbon
skeletons.
Those that are liquid at room temperature are less
dense than water (1.0 g/mL).
They dissolve in each other and in nonpolar organic
solvents.
They are insoluble in water.
4-21
The Acidity of Terminal Alkynes
One of the major differences between the

chemistry of alkynes, and alkanes and alkenes
is that the hydrogen atom of a terminal alkyne is
sufficiently acidic (pKa 25) that it an be removed
by a strong base such as sodium amide, NaNH2,
to give an alkyne anion.
4-22
Because water (pKa 15.7) is a stronger acid

than acetylene or a terminal alkyne,
hydroxide ion is not a strong enough base for
an acid-base reaction with a terminal alkyne.
4-23
The pKa values for alkane and alkene

hydrogens are so large that no base is strong
enough to remove a hydrogen from either of
these classes of compounds.
4-24

How do we account for the acidity of a terminal alkyne
compared to an alkane or alkene?
To answer this question, we must focus on the
stability of the anion derived from each class of
hydrocarbon.
The lone pair of electrons of an alkane anion lies in an
sp3 hybrid orbital, which has 25% s character.
For an alkene anion, the lone pair lies in an sp2 hybrid
orbital, which has 33% s character.
For a terminal alkyne anion, the lone pair lies in an sp
hybrid orbital, which has 50% s character.
4-25
The greater the s character of the orbital

bearing the negative charge, the greater the
stability of the anion, and thus the greater
acidic the hydrogen removed.
Of the series of compounds alkane, alkene,
and alkyne, the carbon of a terminal alkyne is
the most electronegative (50% s character).
Therefore, a terminal alkyne anion is the most
stable of the series, and a terminal alkyne is
the most acidic.
4-26
How to determine the Index of Hydrogen Deficiency

(IHD)
Basis are the Saturated HCs (Alkanes) CnH2n+2

Ex C6H6
4 double bonds
C6H14
3 db & 1 ring
2db & 2 rings
C6 H6
1 db & 3 rings
8 =4
2
H2C C CH CH C CH2
2 triple bonds
HC C CH2
CH2
C CH
4-27
Types of dienes
1. Conjugated diene
2. Isolated diene
3. Cumulative diene
H3C CH C CH CH3
4-28
Alkenes and Alkynes
End Chapter 4
4-29

Chapter 4 - Alkenes and Alkynes

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WILLIAM H.

Alkenes and Alkynes

Unsaturated Hydrocarbon: Contains one or

Arene: benzene and its derivatives (Ch 9)

Benzene and Phenyl Groups

We do not study benzene and its derivatives

The two carbon atoms of a double bond and

According to the orbital overlap model, a

Because of restricted rotation about a CC

The functional group of an alkyne is a carboncarbon triple bond.

IUPAC Nomenclature of alkenes

IUPAC nomenclature of alkenes

Some alkenes, particularly low-molecularweight ones, are known almost exclusively by

IUPAC nomenclature of alkynes

The cis-trans system: Configuration is

2. If priority cannot be assigned on the basis of the atoms bonded

Example: Name each alkene by the E,Z

Alkenes and alkynes are nonpolar compounds.

The physical properties of alkenes and alkynes

The Acidity of Terminal Alkynes

One of the major differences between the

The Acidity of Terminal Alkynes

Because water (pKa 15.7) is a stronger acid

The Acidity of Terminal Alkynes

The pKa values for alkane and alkene

The Acidity of Terminal Alkynes

The Acidity of Terminal Alkynes

The greater the s character of the orbital

How to determine the Index of Hydrogen Deficiency

Basis are the Saturated HCs (Alkanes) CnH2n+2

Alkenes and Alkynes

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